CN112354539A - 用于合成1,3,3,3-四氟丙烯的催化剂及其合成方法 - Google Patents
用于合成1,3,3,3-四氟丙烯的催化剂及其合成方法 Download PDFInfo
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- tetrafluoropropene
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- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- VVWFZKBKXPXGBH-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropane Chemical compound ClC(Cl)CC(Cl)(Cl)Cl VVWFZKBKXPXGBH-UHFFFAOYSA-N 0.000 claims abstract description 24
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract 3
- 239000002994 raw material Substances 0.000 claims description 4
- CDOOAUSHHFGWSA-UPHRSURJSA-N (z)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C/C(F)(F)F CDOOAUSHHFGWSA-UPHRSURJSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002243 precursor Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010606 normalization Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- PNWJILFKWURCIR-UPHRSURJSA-N (e)-1-chloro-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C(Cl)=C/C(F)(F)F PNWJILFKWURCIR-UPHRSURJSA-N 0.000 description 1
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Abstract
本发明用于合成1,3,3,3‑四氟丙烯的催化剂及其合成方法。所公开的催化剂由是活性组分M1、助剂M2和载体组成，所述活性组分M1选自Co3+、Ni2+、Fe3+、Zn2+、Al3+、Cr3+、Mn4+和Cu2+中的一种或几种，助剂M2选自La3+、Ga3+、Ce3+和Zr4+中的一种或几种，所述载体选自Cr2O3、Al2O3或Fe2O3。所公开的方法包括使1,1,1,3,3‑五氯丙烷与氟化氢在存在上述催化剂的条件下在反应区反应以生成1,3,3,3‑四氟丙烯，使用本发明提供的方法可以明显缩短反应路径，降低合成成本，本发明用于1,3,3,3‑四氟丙烯的制备。
Description
技术领域
本发明涉及1,3,3,3-四氟丙烯的合成方法，具体涉及用于合成1,3,3,3-四氟丙烯的催化剂及1,3,3,3-四氟丙烯的一步合成方法。
背景技术
1,3,3,3-四氟丙烯，简称HFO-1234ze，分子式为CF3CH＝CHF，由于不含氯，臭氧消耗潜值(ODP值)为0，大气升温潜值(GWP值)仅为6，大气寿命小于15天，物性与HFC-134a相似，被认为是HFC-134a的理想替代品。
迄今，在已知的众多HFO-1234ze合成方法中，主要是以1,1,1,3,3-五氯丙烷(HCC-240fa)和无水氟化氢为原料反应合成生成目标产物。
中国专利CN101028992公开了以HCC-240fa为原料，采用2个反应器气相氟化法制备HFO-1234ze：第一个反应器主要进行HF氟化HCC-240fa的反应，转化率100％，产物以1-氯-3,3,3-三氟丙烯(HCFC-1233zd)为主；第二个反应器主要进行HCFC-1233zd的氟化反应，产物为HFO-1234ze和少量HFC-245fa。
美国专利US7892494中将HCFC-1233zd与HF在气相进行反应得到1-氯-1,3,3,3-四氟丙烯(HCFC-244fa)和HFC-245fa，然后HCFC-244fa脱HCl，而HFC-245fa脱HF得到HFO-1234ze。
上述现有技术反应路径长，其反应能耗和污染排放物也较大。
发明内容
针对现有技术的缺陷或不足，本发明首先提供一种用于合成1,3,3,3-四氟丙烯的催化剂。
为此，本发明提供的催化剂由是活性组分M1、助剂M2和载体组成，所述活性组分M1选自Co3+、Ni2+、Fe3+、Zn2+、Al3+、Cr3+、Mn4+和Cu2+中的一种或两种以上组合，助剂M2选自La3+、Ga3+、Ce3+和Zr4+中的一种或两种以上组合，所述载体选自Cr2O3、Al2O3或Fe2O3。
可选的，所述活性组分的质量为催化剂总质量的5％～30％。
可选的，所述助剂的质量为催化剂总质量的0.5％～5％。
优选的，所述活性组分为Al3+，所述助剂为La3+，所述载体为Cr2O3。
进一步，本发明提供了1,3,3,3-四氟丙烯的合成方法。为此，本发明所提供的1,3,3,3-四氟丙烯的合成方法包括向填充有催化剂的床层导入气态1,1,1,3,3-五氯丙烷和氟化氢一步反应合成1,3,3,3-四氟丙烯，所述催化剂为上述催化剂。
进一步，所述反应温度为240～300℃，反应床层的氟化氢压力小于等于0.3MPa，氟化氢与1,1,1,3,3-五氯丙烷的摩尔比值为(5～40)：1，反应原料接触时间为3～20s。
进一步，所述1,3,3,3-四氟丙烯包括反式-1,3,3,3-四氟丙烯和顺式-1,3,3,3-四氟丙烯。
本发明的有益效果：本发明与现有技术相比，具有如下有益的技术效果：
①本发明提的催化剂稳定性好，寿命长，在240℃反应时可稳定运行500h。
②现有1,1,1,3,3-五氯丙烷制备HFO-1234ze需经过中间产物HFC-245fa或HCFC-1233zd的过程，本发明提供的1,1,1,3,3-五氯丙烷一步气相氟化制备HFO-1234ze步骤简单，成本低，更具商业化价值。
③本发明的反应温度低，在240℃反应时，1,1,1,3,3-五氯丙烷转化率即可达到100％，同时目标产物HFO-1234ze选择性达到85％。
具体实施方式
除非另有说明，本文中的术语根据相关领域技术人员的常规认识理解。
下面给出本发明的具体实施例，但并不限制本发明的范围。
以下实施例所用试剂、原料、催化剂载体、设备等均为市售产品实施例1：
将10.0g M1的硝酸盐或氯化盐溶解在适量去离子水中得到浸渍液，然后将上述溶液等体积浸渍到50.0g Fe(OH)3载体上，之后常温老化10h后在350℃焙烧处理5h获得M1/Fe2O3前驱体；最后在400℃下对M1/Fe2O3前驱体在氟化氢气氛中进行氟化处理获得M1/Fe2O3催化剂。
取20mL M1/Fe2O3催化剂转入固定床管式反应器中，升温至240℃并干燥2h后通入氟化氢气体，然后通入1,1,1,3,3-五氯丙烷，反应床层的氟化氢压力为0.05MPa，氟化氢与1,1,1,3,3-五氯丙烷的摩尔比为10:1，接触时间为8s，运行12h后产物经水、碱洗吸收氟化氢、氯化氢后进气相色谱仪进行分析，采用面积归一化法计算1,1,1,3,3-五氯丙烷的转化率及目标产物HFO-1234ze选择性。反应结果见表1。
表1
实施例2：
将10.0g M1的硝酸盐或氯化盐溶解在适量去离子水中得到浸渍液，然后将上述溶液等体积浸渍到50.0g拟薄水铝石载体上，之后常温老化10h后在350℃焙烧处理5h获得M1/Al2O3前驱体；最后在400℃下对M1/Al2O3前驱体在氟化氢气氛中进行氟化处理获得M1/Al2O3催化剂。
量取20mL M1/Al2O3催化剂转入固定床管式反应器中，升温至300℃并干燥2h后通入氟化氢气体，然后通入1,1,1,3,3-五氯丙烷，反应床层的氟化氢压力为0.1MPa，氟化氢与1,1,1,3,3-五氯丙烷的摩尔比为5:1，接触时间为20s，运行12h后产物经水、碱洗吸收氟化氢、氯化氢后进气相色谱仪进行分析，采用面积归一化法计算1,1,1,3,3-五氯丙烷的转化率及目标产物HFO-1234ze选择性。反应结果见表2。
表2
实施例3：
将10.0g M1的硝酸盐或氯化盐溶解在适量去离子水中得到浸渍液，然后将上述溶液等体积浸渍到50.0g Cr2O3载体上，之后常温老化10h后在350℃焙烧处理5h获得M1/Cr2O3前驱体；最后在400℃下对M1/Cr2O3前驱体在氟化氢气氛中进行氟化处理获得M1/Cr2O3催化剂。
量取20mL M1/Cr2O3催化剂转入固定床管式反应器中，升温至270℃并干燥2h后通入氟化氢气体，然后通入1,1,1,3,3-五氯丙烷，反应床层的氟化氢压力为0.15MPa，氟化氢与1,1,1,3,3-五氯丙烷的摩尔比为15:1，接触时间为13s，运行12h后产物经水、碱洗吸收氟化氢、氯化氢后进气相色谱仪进行分析，采用面积归一化法计算1,1,1,3,3-五氯丙烷的转化率及目标产物HFO-1234ze选择性。反应结果见表3。
表3
实施例4：
将10.0g硝酸铝和1.0g M2的硝酸盐或氯化盐溶解在适量去离子水中得到浸渍液，然后将上述溶液等体积浸渍到50.0g Cr2O3载体上，之后常温老化10h后在350℃焙烧处理5h获得Al-M2/Cr2O3前驱体；最后在400℃下对Al-M2/Cr2O3前驱体在氟化氢气氛中进行氟化处理获得Al-M2/Cr2O3催化剂。
量取20mL Al-M2/Cr2O3催化剂转入固定床管式反应器中，升温至280℃并干燥2h后通入氟化氢气体，然后通入1,1,1,3,3-五氯丙烷，反应床层的氟化氢压力为0.2MPa，氟化氢与1,1,1,3,3-五氯丙烷的摩尔比为23:1，接触时间为16s，运行12h后产物经水、碱洗吸收氟化氢、氯化氢后进气相色谱仪进行分析，采用面积归一化法计算1,1,1,3,3-五氯丙烷的转化率及目标产物HFO-1234ze选择性。反应结果见表4。
表4
实施例5：
取20mL实施例4制备的Al-La/Cr2O3催化剂转入固定床管式反应器中，升温至290℃并干燥2h后通入氟化氢气体，然后通入1,1,1,3,3-五氯丙烷，反应床层的氟化氢压力为0.3MPa，氟化氢与1,1,1,3,3-五氯丙烷的摩尔比为40:1，接触时间为3s，运行相应时间后产物经水、碱洗吸收氟化氢、氯化氢后进气相色谱仪进行分析，采用面积归一化法计算1,1,1,3,3-五氯丙烷的转化率及目标产物HFO-1234ze选择性。运行时间及相应反应结果见表5。
表5寿命试验评价结果
Claims (8)
1.一种用于合成1,3,3,3-四氟丙烯的催化剂，其特征在于，所述催化剂由是活性组分M1、助剂M2和载体组成，所述活性组分M1选自Co3+、Ni2+、Fe3+、Zn2+、Al3+、Cr3+、Mn4+和Cu2+中的一种或两种以上组合，助剂M2选自La3+、Ga3+、Ce3+和Zr4+中的一种或两种以上组合，所述载体选自Cr2O3、Al2O3或Fe2O3。
2.如权利要求1所述的用于合成1,3,3,3-四氟丙烯的催化剂，其特征在于，所述活性组分的质量为催化剂总质量的5％～30％。
3.如权利要求1所述的用于合成1,3,3,3-四氟丙烯的催化剂，其特征在于，所述助剂的质量为催化剂总质量的0.5％～5％。
4.如权利要求1所述的用于合成1,3,3,3-四氟丙烯的催化剂，其特征在于，所述活性组分为Al3+，所述助剂为La3+，所述载体为Cr2O3。
5.一种1,3,3,3-四氟丙烯的合成方法，其特征在于，向填充有催化剂的床层导入气态1,1,1,3,3-五氯丙烷和氟化氢一步反应合成1,3,3,3-四氟丙烯，所述催化剂为权利要求1-4任一权利要求所述的催化剂。
6.如权利要求5所述的1,3,3,3-四氟丙烯的合成方法，其特征在于，所述反应温度为240～300℃，反应床层的氟化氢压力小于等于0.3MPa，氟化氢与1,1,1,3,3-五氯丙烷的摩尔比值为(5～40)：1，反应原料接触时间为3～20s。
7.如权利要求5所述的1,3,3,3-四氟丙烯的合成方法，其特征在于，所述1,3,3,3-四氟丙烯包括反式-1,3,3,3-四氟丙烯和顺式-1,3,3,3-四氟丙烯。
8.如权利要求5所述的1,3,3,3-四氟丙烯的合成方法，其特征在于，所述1,3,3,3-四氟丙烯为反式-1,3,3,3-四氟丙烯。
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